The present invention relates to crystalline inorganic materials containing at least one Group VIII metallo element selected from the group consisting of cobalt and nickel, aluminum, boron and oxygen having specified X-ray patterns. This invention also relates to solid inorganic materials containing at least one Group VIII metallo element, aluminum, boron and oxygen made by calcining a mixture comprising sources of divalent metallo ions, alumina and boria at elevated temperature, and the use of such solid in catalytic compositions for the conversion of organic compounds, particularly hydrogenation of hydrocarbons and oxygen containing hydrocarbons, dehydrogenation to functionalize alkylaromatic compounds, isomerization of alkylaromatic compounds, oligomerization of olefins, and oxidation of hydrocarbons and oxygen containing hydrocarbons.
The use of an active metallo element or a supported metallo element composition containing aluminum and boron as a conversion catalyst is known in the art. U.S. Pat. No. 3,883,442 to McArthur is illustrative of prior art disclosing the superiority of a supported active metal catalyst to resist shrinkage at high temperatures (up to 1600.degree. C.) by stabilization of a preformed alumina catalyst support. McArthur states stabilization was achieved by impregnating an alumina support with a solution of a boron compound which is thermally decomposable to B.sub.2 O.sub.3, followed by drying and calcining of the impregnated support at temperatures below about 1500.degree. C., but sufficiently high to decompose the boron compound. McArthur also discloses that the most commonly used technique of preparing a supported metallo element catalyst involved: following calcination, impregnating in conventional manner the alumina support material containing some retained B.sub.2 O.sub.3 with a solution of the desired metal salt, preferably those that are thermally decomposable to give the corresponding metal oxides and/or sulfides, and calcining the salt-impregnated support to convert the impregnated salt to the active catalytic form. McArthur neither discloses nor suggests a mixed oxide composition of a metallo element, aluminum, and boron.
In U.S. Pat. No. 3,954,670 to Pine a boria-alumina based catalyst is disclosed in the combination of a metallo element and a boria-alumina catalyst support materials prepared by hydrolysis of a mixture of aluminum alkoxide and boron alkoxide in the presence of water at a temperature in the range of 20.degree. to 100.degree. C. The disclosed catalyst compositions, said to be useful for desulfurization, denitrogenation, reforming and other hydrocarbon conversion processes, included both cobalt and nickel as metallo elements in combinations with the boria-alumina catalyst composition disclosed in Pine and, optionally, a crystalline aluminosilicate zeolite with or without rare earth elements. However, Pine neither discloses nor suggests any crystalline mixed oxide composition of a metallo element, aluminum, and boron.
Zletz in U.S. Pat. No. 4,729,979, which is hereby incorporated by reference, discusses the characteristics of a good catalyst and/or catalyst support and a new crystalline copper aluminum borate characterized by a specific X-ray diffraction pattern, surface area and pore volume which is at least partially reducible with hydrogen at a temperature no more than 350.degree. C. to a composition containing zero valent copper and Al.sub.4 B.sub.2 O.sub.9. Satek in U.S. Pat. No. 4,590,324, which is hereby incorporated by reference, discusses using the new crystalline copper aluminum borate as a catalyst to dehydrogenate alkylaromatics to alkenylaromatics. Zletz et al. in U.S. Pat. No. 4,645,753, which is hereby incorporated by reference, discusses doping the new crystalline copper aluminum borate to contain an alkali metal or alkaline earth metal element for use as a catalyst to dehydrogenate alkylaromatics to alkenylaromatics. The Zletz, Satek, and Zletz et al. patents alone or in combination neither disclose nor suggest a mixed oxide composition of aluminum, boron, and a metallo element without copper. Furthermore, these patents disclose crystalline copper aluminum borate having significant X-ray diffraction lines which are substantially different from X-ray diffraction patterns for crystalline materials of the present invention.
Schwab and Bertaut disclose the preparation of a single crystal of a boroaluminate of nickel in Bull. Soc. Fr. Mineral. Cristollogr. (1970), 93, 255-257, "Structure di boroaluminate B.sub.2 O.sub.3.Al.sub.2 O.sub.3.4NiO" which is hereby incorporated by reference, by mixing the oxides B.sub.2 O.sub.3, Al.sub.2 O.sub.3 and NiO in the mol ratio of 1:1:4 plus a large excess of B.sub.2 O.sub.3 [sic], heating the mixture to 1300.degree. C., cooling the hot mixture carefully to room temperature at a rate of 50.degree. C. per hour, and treating the cooled product with dilute nitric acid to dissolve excess borax providing single crystals about 2-3 mm long. The atomic coordinates for a single crystal structure are reported, however no powder x-ray diffraction pattern is reported. Boroaluminates of nickel produced by the indicated route are believed to be well-defined, dense crystalline particles which have an extremely low surface area due to heating a mixture of oxides to a temperature of 1300.degree. C.
The general object of the present invention is to provide a new composition useful as a catalyst to convert organic compounds to other compounds.
Another general object of this invention is to produce a new catalyst which is useful to hydrogenate hydrocarbons and oxygen containing hydrocarbons, dehydrogenate alkylaromatic compounds, isomerize alkylaromatic compounds, oligomerize olefins, and oxidize hydrocarbons, particularly aromatic hydrocarbons.
Other objects and advantages of the invention will become apparent upon reading the following detailed description and appended claims.